JP2012159651A - Photosensitive resin composition and use thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition facilitating control of a developing solution or a stripping solution and having excellent dispersibility in a developing solution.SOLUTION: There is provided a photosensitive resin composition comprising: (a) an alkali-soluble thermoplastic polymer of 20 to 90 mass%; (b) an addition polymerizable monomer having at least one polymerizable ethylenically unsaturated bond in a molecule of 5 to 75 mass%; (c) a photopolymerization initiator of 0.01 to 30 mass% and (d) a compound represented by general formula [I]:R-O-(A-O)-H of 0.01 to 30 mass%. In the formula, R1 represents a monovalent organic group having 1 to 8 carbon atoms; Arepresents an alkylene group; n1 represents an integer of 1 or more and 60 or less; and the repeated structure of -(A-O)- may be the same or different, and when the repeated structure of -(A-O)- is different from one another, the structure may be a random or block structure.

Description

  The present invention relates to a photosensitive resin composition that can be developed with an alkaline aqueous solution, a photosensitive resin laminate obtained by laminating the photosensitive resin composition on a support, and a substrate using the photosensitive resin laminate. The present invention relates to a method for forming a resist pattern and a use of the resist pattern. More specifically, the present invention relates to a photosensitive resin composition that provides a resist pattern suitable for manufacturing a printed wiring board, a flexible printed wiring board, and the like.

  Conventionally, printed wiring boards are manufactured by a photolithography method. The photolithographic method is a method in which a photosensitive resin composition is applied onto a substrate, pattern exposure is performed to polymerize and cure an exposed portion of the photosensitive resin composition, and an unexposed portion is removed with a developer to form a resist on the substrate. It refers to a method of forming a conductor pattern on a substrate by forming a pattern, performing etching or plating treatment to form a conductor pattern, and then removing the resist pattern from the substrate.

  In the photolithography method described above, when the photosensitive resin composition is applied onto the substrate, the photosensitive resin composition solution is applied to the substrate and dried, or the support and the layer made of the photosensitive resin composition (Hereinafter also referred to as “photosensitive resin layer”) and a photosensitive resin laminate (hereinafter also referred to as “dry film resist”) obtained by sequentially laminating a protective layer as necessary, are laminated on a substrate. One of the methods is used. In the production of printed wiring boards, the latter dry film resist is often used.

  A method for producing a printed wiring board using the dry film resist will be briefly described below.

  First, when the dry film resist has a protective layer such as a polyethylene film, it is peeled off from the photosensitive resin layer. Next, the photosensitive resin layer and the support are laminated on a substrate such as a copper clad laminate using a laminator so that the substrate, the photosensitive resin layer, and the support are in this order. Next, the exposed portion is polymerized and cured by exposing the photosensitive resin layer to ultraviolet rays including i-line (365 nm) emitted from an ultrahigh pressure mercury lamp through a photomask having a wiring pattern. Next, the support made of polyethylene terephthalate or the like is peeled off.

  Next, a non-exposed portion of the photosensitive resin layer is dissolved or dispersed and removed by a developing solution such as an aqueous solution having weak alkalinity to form a resist pattern on the substrate. Next, a known etching process or pattern plating process is performed using the formed resist pattern as a protective mask. In the method of removing a metal portion by etching, a metal in the hole is prevented from being etched by covering a through hole (through hole) of the substrate or a via hole for interlayer connection with a cured resist film. This construction method is called a tenting method. For the etching step, for example, cupric chloride, ferric chloride or a copper ammonia complex solution is used.

  Finally, the resist pattern is peeled from the substrate with an alkaline aqueous solution such as sodium hydroxide to produce a substrate having a conductor pattern, that is, a printed wiring board. In the method of pattern plating, copper plating is performed on the same copper surface, and if necessary, after further plating of solder, nickel, tin, etc., the resist pattern is peeled off from the substrate in the same manner. The copper surface such as the copper clad laminate that appears is etched.

  Therefore, the dry film resist is an important element for meeting the demand for higher density of printed wiring boards and increasing demand, and higher resolution, higher adhesion, higher workability and higher performance than conventional dry films. There is a demand for the development of products that can yield.

  However, when an alkali development type dry film resist in which an unexposed portion is dissolved or dispersed with a developing solution such as a weak alkaline aqueous solution is used, an unpolymerized composition is dispersed in the developing solution, and this dispersion is collected. And agglomerates in the developer or cause foaming of the developer. Aggregates reattach to the substrate during the development process and cause defects. In addition, when the developer is circulated through the filter in order to prevent the occurrence of defects, the frequency of filter replacement increases or the cleaning interval of the developing machine becomes shorter if a large amount of aggregates are generated. The problem is occurring. The foaming of the developer hinders the spray of the developer from being uniformly applied during the development process and causes a defect. In addition, the foaming of the developer also causes a management problem that a special antifoaming agent is required to suppress foaming.

  Also, in the process of peeling the resist pattern from the substrate after etching, there may be a problem that the stripping solution foams due to components eluted from the resist. In this case as well, there arises a problem in yield due to the fact that the spray is not uniformly applied due to foaming, or a management problem that requires a special antifoaming agent or makes it difficult to change the liquid. Sometimes.

  For example, in order to reduce development aggregates, in the photosensitive resin composition comprising an alkali-soluble polymer, a photopolymerizable monomer and a photopolymerization initiator, the alkali-soluble polymer, the photopolymerizable monomer and the photopolymerization initiator are: There is provided a dry film resist obtained by laminating a photosensitive resin composition characterized in that it is blended in a specific mass% and further contains a specific compound (Patent Document 1).

  However, a new dry film resist that can further suppress the foaming of the developer and the foaming of the stripping solution is still desired.

JP2002-365797

  The problem to be solved by the present invention is a photosensitive resin composition that is particularly excellent in developing solution dispersibility in an unexposed portion as a resist material such as an etching resist or a plating resist, and that can suppress foaming of the developing solution and the stripping solution. , A photosensitive resin laminate using the photosensitive resin composition, a method for producing a resist pattern on the substrate using the photosensitive resin laminate, and the photosensitive resin laminate It is to provide a method for producing a conductor pattern, a printed wiring board and the like.

  The above problems can be solved by the following configuration of the present invention. That is, the present invention is as follows:

[1] (a) alkali-soluble thermoplastic polymer: 20 to 90% by mass, (b) addition polymerizable monomer having at least one polymerizable ethylenically unsaturated bond in the molecule: 5 to 75% by mass, ( c) Photopolymerization initiator: 0.01 to 30% by mass, and (d) the following general formula [I]
_{R 1 -O- (A 1 -O)} n1 -H [I]
{Wherein, R ₁ is a monovalent organic group having 1 to 8 carbon atoms, A ₁ is an alkylene group, n 1 is an integer of 1 to 60, and — (A ₁ — The repeating structure of O) — may be the same or different, and may be random or block if the repeating structure of — (A ₁ —O) — is different. } A compound represented by: A photosensitive resin composition containing 0.01 to 30% by mass.

｛式中、Ｒ_２及びＲ_３は、各々独立にＨ又はＣＨ_３であり、Ａ_２は、−ＣＨ（ＣＨ_３）ＣＨ_２−、−ＣＨ_２ＣＨ（ＣＨ_３）−及び／又は−ＣＨ_２ＣＨ_２−であり、ｎ_２及びｎ_３は、各々独立に１以上の整数であり、ｎ_２＋ｎ_３は、２〜６０の整数であり、そして−（Ａ_２−Ｏ）−の繰り返し構造は、ランダム又はブロックでよい。｝で表されるビスフェノールＡ系（メタ）アクリレート化合物である、［１］に記載の感光性樹脂組成物。 [2] The addition polymerizable monomer (b) having at least one polymerizable ethylenically unsaturated bond in the molecule is represented by the following general formula [II]:

{Wherein R ₂ and R ₃ are each independently H or CH ₃ , and A ₂ is —CH (CH ₃ ) CH ₂ —, —CH ₂ CH (CH ₃ ) — and / or —CH _2. CH ₂ —, n ₂ and n ₃ are each independently an integer of 1 or more, n ₂ + n ₃ is an integer of 2 to 60, and the repeating structure of — (A ₂ —O) — is Random or block. } The photosensitive resin composition as described in [1] which is a bisphenol A type | system | group (meth) acrylate compound represented by these.

  [3] The photosensitive resin composition according to [1] or [2], wherein the (a) alkali-soluble thermoplastic polymer contains at least a monomer having styrene and an ethylenic double bond as components.

  [4] A photosensitive resin laminate comprising a support and a layer comprising the photosensitive resin composition according to any one of [1] to [3].

  [5] A method for forming a resist pattern, including a step of forming a resist pattern using the photosensitive resin laminate according to [4].

  [6] A method for producing a printed wiring board, comprising a step of forming a resist pattern on a circuit forming substrate using the photosensitive resin laminate according to [4].

  According to the present invention, the developer dispersibility of the unexposed portion is excellent, the foaming when the photosensitive resin composition is dissolved in the developer can be suppressed, and the foaming of the stripping solution can be suppressed even in the stripping process. A resin composition, a photosensitive resin laminate using the photosensitive resin composition, and a method for forming a resist pattern using the photosensitive resin laminate can be provided. Moreover, it becomes possible to manufacture substrates, such as a printed wiring board, using this photosensitive resin laminated body.

Hereinafter, the present invention will be specifically described.
<Photosensitive resin composition>
The photosensitive resin composition according to the present invention comprises (a) an alkali-soluble thermoplastic polymer: 20 to 90% by mass, (b) an addition polymerizable monomer having at least one polymerizable ethylenically unsaturated bond in the molecule. (Hereinafter also simply referred to as “addition polymerizable monomer”): 5 to 75% by mass, (c) Photopolymerization initiator: 0.01 to 30% by mass as an essential component, and (d) the following general formula [I]
_{R 1 -O- (A 1 -O)} n1 -H [I]
{Wherein, R ₁ is a monovalent organic group having 1 to 8 carbon atoms, A ₁ is an alkylene group, n 1 is an integer of 1 to 60, and — (A ₁ — The repeating structure of O) — may be the same or different, and may be random or block if the repeating structure of — (A ₁ —O) — is different. }
The compound which consists of: It is characterized by including 0.01-30 mass%.

(A) Alkali-soluble thermoplastic polymer (a) The alkali-soluble thermoplastic polymer has an α, β-unsaturated carboxyl group-containing monomer as a polymerization component, and the acid equivalent of the alkali-soluble thermoplastic polymer is 100 to 100 Preferably, the weight average molecular weight is 600 and the weight average molecular weight is 5,000 to 500,000. The carboxyl group in the alkali-soluble thermoplastic polymer is necessary for the photosensitive resin composition according to the present invention to have developability or releasability with respect to a developer or stripper composed of an aqueous alkali solution. The acid equivalent refers to the mass of the alkali-soluble resin having 1 equivalent of a carboxyl group therein. A more preferable lower limit of the acid equivalent is 250, and a more preferable upper limit is 450. (A) The acid equivalent of the alkali-soluble thermoplastic polymer is improved in development resistance, resolution and adhesion, and further in the solvent or other components in the photosensitive resin composition, particularly (b) addition described later. 100 or more is preferable from the viewpoint of ensuring compatibility with the polymerizable monomer, and 600 or less is preferable from the viewpoint of improving developability and peelability. The acid equivalent is measured by a potentiometric titration method using Hiranuma automatic titrator (COM-555) manufactured by Hiranuma Sangyo Co., Ltd. and 0.1 mol / L sodium hydroxide.

  (A) As for the weight average molecular weight of an alkali-soluble thermoplastic polymer, 5,000-500,000 are preferable. The weight average molecular weight is determined from the viewpoint of maintaining a uniform thickness of the photosensitive resin laminate (dry film resist) to obtain resistance to the developer, and from the end face of the roll when the photosensitive resin laminate is wound into a roll. 5,000 or more is preferable from the viewpoint of the phenomenon that the photosensitive resin composition exudes, that is, edge fuse is suppressed, and 500,000 or less is preferable from the viewpoint of maintaining developability. More preferably, (a) the lower limit of the weight average molecular weight of the alkali-soluble thermoplastic polymer is 20,000, and (a) the upper limit of the weight average molecular weight of the alkali-soluble thermoplastic polymer is 250,000. The weight average molecular weight in the present specification means a weight average molecular weight measured by gel permeation chromatography (GPC) using a calibration curve of polystyrene (Shodex STANDARD SM-105 manufactured by Showa Denko KK).

(A) The weight average molecular weight of the alkali-soluble thermoplastic polymer can be measured using gel permeation chromatography manufactured by JASCO Corporation under the following conditions:
Differential refractometer: RI-1530
Pump: PU-1580
Degasser: DG-980-50
Column oven: CO-1560
Column: KF-8025, KF-806M × 2, KF-807 in order
Eluent: THF.

  The (a) alkali-soluble thermoplastic polymer is preferably a (co) polymer containing as a component one or more monomers selected from the first or second monomer described below.

  The first monomer is a carboxylic acid or acid anhydride having one polymerizable unsaturated group in the molecule. Examples include (meth) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic anhydride, and maleic acid half ester. Among these, (meth) acrylic acid is particularly preferable.

  The second monomer is a monomer that is non-acidic and has at least one polymerizable unsaturated group in the molecule. For example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, Esters of vinyl alcohol such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, vinyl acetate, (meta ) Acrylonitrile, styrene, and polymerizable styrene derivatives. Among these, methyl (meth) acrylate, n-butyl (meth) acrylate, styrene, and benzyl (meth) acrylate are preferable, and it is particularly preferable to use styrene from the viewpoint of resolution.

  (A) The alkali-soluble thermoplastic polymer is prepared by mixing the above monomers and diluting with a solvent such as acetone, methyl ethyl ketone, or isopropanol, and adding a radical polymerization initiator such as benzoyl peroxide, azoisobutyrate. It is preferable to synthesize by adding a suitable amount of nitrile and stirring with heating. In some cases, the synthesis is performed while a part of the mixture is dropped into the reaction solution. After completion of the reaction, a solvent may be further added to adjust to a desired concentration. As synthesis means, bulk polymerization, suspension polymerization, or emulsion polymerization may be used in addition to solution polymerization.

  Particularly preferred (a) alkali-soluble thermoplastic polymer has a copolymerization ratio of the first monomer and the second monomer of 10 to 60% by mass of the first monomer and the second monomer. A body is 40-90 mass%, More preferably, a 1st monomer is 15-35 mass%, and a 2nd monomer is 65-85 mass%.

  (A) As a more specific example of the alkali-soluble thermoplastic polymer, a copolymer containing methyl methacrylate, methacrylic acid and styrene as copolymerization components, methyl methacrylate, methacrylic acid and n-butyl acrylate are copolymerized Examples thereof include a polymer containing as a component, and a polymer containing benzyl methacrylate, methyl methacrylate and 2-ethylhexyl acrylate as a copolymer component.

  The content of the (a) alkali-soluble thermoplastic polymer in the photosensitive resin composition of the present invention is in the range of 20 to 90% by mass based on the total solid content of the photosensitive resin composition, preferably It is 40-60 mass%. (A) The content of the alkali-soluble thermoplastic polymer maintains the alkali developability of the photosensitive resin composition, and the resist pattern formed by exposure and development has characteristics as a resist, such as tenting, etching and the like. 20 mass% or more is preferable from a viewpoint that it has sufficient tolerance in various plating processes, and 90 mass% or less is preferable from the viewpoint that the photosensitive resin composition before curing and the resist pattern after curing have sufficient flexibility.

(B) Addition polymerizable monomer (b) The addition polymerizable monomer is a compound having at least one polymerizable ethylenically unsaturated bond in the molecule. The ethylenically unsaturated bond is preferably a terminal ethylenically unsaturated group. Furthermore, it is preferable to use at least one bisphenol A-based (meth) acrylate compound as the (b) addition polymerizable monomer from the viewpoint of high resolution, edge fuse properties, and tenting properties.

｛式中、Ｒ_２及びＲ_３は、各々独立にＨ又はＣＨ_３であり、Ａ_２は、−ＣＨ（ＣＨ_３）ＣＨ_２−、−ＣＨ_２ＣＨ（ＣＨ_３）−及び／又は−ＣＨ_２ＣＨ_２−であり、ｎ_２及びｎ_３は、各々独立に１以上の整数であり、好ましくはｎ_２及びｎ_３は、各々独立に１〜３０の整数であり、ｎ_２＋ｎ_３は、２〜６０の整数であり、そして−（Ａ_２−Ｏ）−の繰り返し構造は、ランダム又はブロックでよい。｝で表される。 In this specification, the bisphenol A-based (meth) acrylate compound means a (meth) acryloyl group or a carbon-carbon unsaturated double bond derived from a (meth) acryloyl group and —C ₆ H ₄ — derived from bisphenol A. A compound having a C (CH ₃ ) ₂ —C ₆ H ₄ — group, and represented by the following general formula [II]:

{Wherein R ₂ and R ₃ are each independently H or CH ₃ , and A ₂ is —CH (CH ₃ ) CH ₂ —, —CH ₂ CH (CH ₃ ) — and / or —CH _2. CH ₂ —, n ₂ and n ₃ are each independently an integer of 1 or more, preferably n ₂ and n ₃ are each independently an integer of 1 to 30, and n ₂ + n ₃ is 2 It is an integer of ˜60, and the repeating structure of — (A ₂ —O) — may be random or block. }.

  Specific examples of the unsaturated compound represented by the above general formula [II] include polyethylene glycol dimethacrylate (NK ester manufactured by Shin-Nakamura Chemical Co., Ltd.) with an average of 2 units of ethylene oxide added to both ends of bisphenol A. BPE-200) or polyethylene glycol dimethacrylate (NK ester BPE-500 manufactured by Shin-Nakamura Chemical Co., Ltd.) with an average of 5 units of ethylene oxide added to both ends of bisphenol A and 6 units on average of both ends of bisphenol A Of polyalkylene glycol with an average of 2 units of propylene oxide and polyalkylene glycol with an average of 15 units of ethylene oxide and an average of 2 units of propylene oxide on both ends of bisphenol A. Call of dimethacrylate and the like.

  (B) As addition polymerizable monomers, known compounds having at least one ethylenically unsaturated group can be used in addition to the above compounds. For example, 4-nonylphenylheptaethylene glycol dipropylene glycol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, phenoxyhexaethylene glycol acrylate, a reaction product of a half ester compound of phthalic anhydride and 2-hydroxypropyl acrylate and propylene oxide (Nippon Shokubai Chemical Co., Ltd., trade name OE-A 200),

  4-normal octyl phenoxypentapropylene glycol acrylate, 1,6-hexanediol (meth) acrylate, 1,4-cyclohexanediol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, etc. Polyoxyalkylene glycol di (meth) acrylate, 2-di (p-hydroxyphenyl) propane di (meth) acrylate, glycerol tri (meth) acrylate, pentaerythritol penta (meth) acrylate, trimethylolpropane triglycidyl ether tri (meth) Acrylate,

  2,2-bis (4-methacryloxypentaethoxyphenyl) propane, polyfunctional group (meth) acrylates containing urethane groups such as urethanized products of hexamethylene diisocyanate and nonapropylene glycol monomethacrylate, and many isocyanuric acid ester compounds A functional (meth) acrylate etc. are mentioned. These may be used singly or in combination of two or more, and may be used in combination with a bisphenol A (meth) acrylate compound or a compound represented by the above general formula [II].

  The content of the (b) addition polymerizable monomer in the photosensitive resin composition according to the present invention is in the range of 5 to 75% by mass based on the total solid content of the photosensitive resin composition, more preferably, It is 15-70 mass%. (B) The content of the addition polymerizable monomer is 5% by mass or more from the viewpoint of resolution, adhesion and copper line formability, and 75% by mass or less from the viewpoint of flexibility of the cured film. .

(C) Photopolymerization initiator As the photopolymerization initiator, those usually used as photopolymerization initiators for photosensitive resins can be used as appropriate, and in particular, hexaarylbisimidazole (hereinafter also referred to as triarylimidazolyl dimer). .) Is preferably used.

  Examples of the triarylimidazolyl dimer include 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer (hereinafter referred to as “2,2′-bis (2-chlorophenyl) -4,4 ′, 5”). , 5′-tetraphenyl-1,1′-bisimidazole ”), 2,2 ′, 5-tris- (o-chlorophenyl) -4- (3,4-dimethoxyphenyl) -4 ′, 5 '-Diphenylimidazolyl dimer, 2,4-bis- (o-chlorophenyl) -5- (3,4-dimethoxyphenyl) -diphenylimidazolyl dimer,

  2,4,5-tris- (o-chlorophenyl) -diphenylimidazolyl dimer, 2- (o-chlorophenyl) -bis-4,5- (3,4-dimethoxyphenyl) -imidazolyl dimer, 2, 2′-bis- (2-fluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2′-bis- (2,3-difluoromethyl) Phenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2′-bis- (2,4-difluorophenyl) -4,4 ′, 5 5′-tetrakis- (3-methoxyphenyl) -imidazolyl dimer,

  2,2′-bis- (2,5-difluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2′-bis- (2, 6-difluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2′-bis- (2,3,4-trifluorophenyl) -4 , 4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2′-bis- (2,3,5-trifluorophenyl) -4,4 ′, 5,5 '-Tetrakis- (3-methoxyphenyl) -imidazolyl dimer,

  2,2′-bis- (2,3,6-trifluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2′-bis- (2,4,5-trifluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2′-bis- (2,4,6- Trifluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -imidazolyl dimer,

  2,2′-bis- (2,3,4,5-tetrafluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2′- Bis- (2,3,4,6-tetrafluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, and 2,2′-bis- (2 , 3,4,5,6-pentafluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -imidazolyl dimer.

  In particular, 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer is a photopolymerization initiator having a high effect on resolution or the strength of a cured resist film, and is preferably used. These may be used alone or in combination of two or more. Further, it can be used in combination with the following acridine compounds, pyrazoline compounds and the like.

  In a preferred embodiment of the present invention, (c) an acridine compound or a pyrazoline compound is used as a photopolymerization initiator. Examples of acridine compounds include acridine, 9-phenylacridine, 9- (4-tolyl) acridine, 9- (4-methoxyphenyl) acridine, 9- (4-hydroxyphenyl) acridine, 9-ethylacridine, 9-chloroethyl. Acridine, 9-methoxyacridine, 9-ethoxyacridine,

  9- (4-methylphenyl) acridine, 9- (4-ethylphenyl) acridine, 9- (4-n-propylphenyl) acridine, 9- (4-n-butylphenyl) acridine, 9- (4-tert -Butylphenyl) acridine, 9- (4-ethoxyphenyl) acridine, 9- (4-acetylphenyl) acridine, 9- (4-dimethylaminophenyl) acridine, 9- (4-chlorophenyl) acridine,

  9- (4-bromophenyl) acridine, 9- (3-methylphenyl) acridine, 9- (3-tert-butylphenyl) acridine, 9- (3-acetylphenyl) acridine, 9- (3-dimethylaminophenyl) ) Acridine, 9- (3-diethylaminophenyl) acridine, 9- (3-chlorophenyl) acridine, 9- (3-bromophenyl) acridine, 9- (2-pyridyl) acridine, 9- (3-pyridyl) acridine, 9- (4-pyridyl) acridine is mentioned. Of these, 9-phenylacridine is preferable.

  Examples of the pyrazoline compound include 1-phenyl-3- (4-tert-butyl-styryl) -5- (4-tert-butyl-phenyl) -pyrazoline, 1- (4- (benzoxazol-2-yl) phenyl) -3- (4-tert-butyl-styryl) -5- (4-tert-butyl-phenyl) -pyrazoline, 1-phenyl-3- (4-biphenyl) -5- (4-tert-butyl-phenyl) -Pyrazolin, 1-phenyl-3- (4-biphenyl) -5- (4-tert-octyl-phenyl) -pyrazoline is preferred.

  As photopolymerization initiators other than the above, for example, 2-ethylanthraquinone, octaethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloro Quinones such as anthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone, and 3-chloro-2-methylanthraquinone,

  Aromatic ketones such as benzophenone, Michler's ketone [4,4′-bis (dimethylamino) benzophenone], and 4,4′-bis (diethylamino) benzophenone, benzoin, benzoin ethyl ether, benzoin phenyl ether, methylbenzoin, and ethyl Benzoin ethers such as benzoin,

  Benzyl dimethyl ketal, benzyl diethyl ketal, combinations of thioxanthones and alkylaminobenzoic acid, 1-phenyl-1,2-propanedione-2-O-benzoinoxime, 1-phenyl-1,2-propanedione-2- ( And oxime esters such as (O-ethoxycarbonyl) oxime.

  Examples of the combination of the above thioxanthones and alkylaminobenzoic acid include, for example, a combination of ethylthioxanthone and ethyl dimethylaminobenzoate, a combination of 2-chlorothioxanthone and ethyl dimethylaminobenzoate, and isopropylthioxanthone and dimethylaminobenzoic acid. A combination with ethyl acid is mentioned. N-aryl amino acids may also be used. Examples of N-aryl amino acids include N-phenylglycine, N-methyl-N-phenylglycine, N-ethyl-N-phenylglycine and the like. Among these, N-phenylglycine is particularly preferable.

  Content of (c) photoinitiator in the photosensitive resin composition of this invention is the range of 0.01-30 mass% on the basis of the total solid of the photosensitive resin composition, and a more preferable minimum Is 0.05% by mass, a more preferable lower limit is 0.1% by mass, a more preferable upper limit is 15% by mass, and a further preferable upper limit is 10% by mass. (C) The content of the photopolymerization initiator is 0.01% by mass or more from the viewpoint of obtaining sufficient sensitivity at the time of photopolymerization by exposure, and the bottom surface of the photosensitive resin composition at the time of photopolymerization (that is, a portion far from the light source) From the viewpoint of sufficiently transmitting light up to) and obtaining good resolution and adhesion, it is 30% by mass or less.

(D) Compound represented by general formula [I] The photosensitive resin composition according to the present invention comprises (d) general formula [I]:
_{R 1 -O- (A 1 -O)} n1 -H [I]
{Wherein, R ₁ is a monovalent organic group having 1 to 8 carbon atoms, A ₁ is an alkylene group, n 1 is an integer of 1 to 60, and — (A ₁ — The repeating structure of O) — may be the same or different, and may be random or block if the repeating structure of — (A ₁ —O) — is different. }
It is necessary to contain 1 type, or 2 or more types of compounds represented by these.

(D) In the compound represented by the general formula [I], R ₁ is a monovalent organic group. Specific examples include a substituted or unsubstituted alkyl group, a phenyl group, and an acyl group. From the viewpoint of aggregation, an unsubstituted alkyl group is particularly preferable. From the viewpoint of antifoaming properties, the number of carbon atoms is more preferably 8 or less, and particularly preferably 7 or less. Further, when R ₁ is an unsubstituted alkyl group, the number of carbon atoms is preferably 2 or more, and more preferably 3 or more, from the viewpoints of handleability and antifoaming properties. Specifically, examples of the unsubstituted alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, an octyl group, and a 2-ethylhexyl group.

(D) In the compound represented by the above general formula [I], A ₁ is an alkylene group. The number of carbon atoms of the alkylene group is preferably 2 or more from the viewpoint of handleability, and preferably 4 or less from the viewpoint of compatibility with other raw materials. Specifically, the alkylene _{group, -CH 2 CH 2 CH 2 CH} 2 -, - CH 2 CH 2 CH 2 -, - CH (CH 3) CH 2 -, - CH 2 CH (CH 3) -, —CH ₂ CH ₂ — and the like can be mentioned, among which —CH (CH ₃ ) CH ₂ — or —CH ₂ CH (CH ₃ ) — is preferable.

The repeating units of — (A ₁ —O) — may be the same or different. - (A 1 _-O) - if the different repeating units, the structure may be random or block. Further, n1 representing the number of repetitions may be an integer of 1 or more and 60 or less, preferably 4 or more, and more preferably 10 or more from the viewpoint of storage stability. Moreover, 45 or less are preferable and 25 or less are more preferable from compatibility with another raw material.

  These compounds represented by the above general formula [I] may be used alone or in combination of two or more. Content of the compound shown by general formula [I] in the photosensitive resin composition of this invention is the range of 0.01-30 mass% on the basis of the total solid of the photosensitive resin composition, and more A preferable lower limit is 0.05% by mass, a more preferable lower limit is 0.1% by mass, a more preferable upper limit is 15% by mass, and a further preferable upper limit is 10% by mass. The content of the compound represented by the general formula [I] is 0.01% by mass or more in order to sufficiently obtain the defoaming effect of the developer and the stripping solution, and 30% by mass or less in order to maintain the resist performance. It is.

  When the photosensitive resin composition of the present invention contains the compound represented by the above general formula [I], the dispersibility of the developer in the unexposed area is particularly excellent, and the foaming of the developer and the stripping solution can be suppressed. it can.

(E) Other additives The photosensitive resin composition of the present invention may contain various additives in addition to the components (a) to (d). Specifically, for example, coloring substances such as dyes and pigments are included. Examples of such coloring substances include phthalocyanine green, crystal violet, methyl orange, Nile blue 2B, Victoria blue, malachite green, basic blue 20, diamond green, and the like.

  When the coloring material is contained, the addition amount of the coloring material is preferably 0.001 to 1% by mass based on the total solid content of the photosensitive resin composition. When the addition amount of the coloring substance is 0.001% by mass or more, there is an effect of improving the handleability, and when it is 1% by mass or less, there is an effect of maintaining the storage stability.

  Moreover, you may contain the color former in the photosensitive resin composition so that a visible image can be given by exposure. Examples of such a coloring dye include a leuco dye or a combination of a fluorane dye and a halogen compound.

  For example, as leuco dyes, tris (4-dimethylamino-2-methylphenyl) methane [leucocrystal violet], tris (4-dimethylamino-2-methylphenyl) methane [leucomalachite green], and fluorane dye Is mentioned. Among these, when leuco crystal violet is used, the contrast is good and preferable.

  Examples of the halogen compound include amyl bromide, isoamyl bromide, isobutylene bromide, ethylene bromide, diphenylmethyl bromide, benzal bromide, methylene bromide, tribromomethylphenyl sulfone, carbon tetrabromide, tris (2, 3-dibromopropyl) phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,1-trichloro-2,2-bis (p-chlorophenyl) ethane, hexachloroethane, chlorinated triazine compounds and the like.

  When these dyes are contained, the content of the dye in the photosensitive resin composition of the present invention is preferably 0.1 to 10% by mass based on the total solid content of the photosensitive resin composition.

  Furthermore, in order to improve the thermal stability and storage stability of the photosensitive resin composition, at least one compound selected from the group consisting of radical polymerization inhibitors or benzotriazoles and carboxybenzotriazoles is photosensitive. It is preferable to make it contain in a resin composition.

  Examples of such radical polymerization inhibitors include p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, tert-butylcatechol, cuprous chloride, 2,6-di-tert-butyl-p-cresol, 2,2 Examples include '-methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), nitrosophenylhydroxyamine aluminum salt, and diphenylnitrosamine.

  Examples of benzotriazoles include 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, bis (N-2-ethylhexyl) aminomethylene-1,2,3-benzotriazole, Examples thereof include bis (N-2-ethylhexyl) aminomethylene-1,2,3-tolyltriazole and bis (N-2-hydroxyethyl) aminomethylene-1,2,3-benzotriazole.

  Examples of carboxybenzotriazoles include 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, (N, N-dibutylamino) carboxybenzotriazole, N- ( N, N-di-2-ethylhexyl) aminomethylenecarboxybenzotriazole, N- (N, N-di-2-hydroxyethyl) aminomethylenecarboxybenzotriazole, N- (N, N-di-2-ethylhexyl) amino And ethylene carboxybenzotriazole.

  The total addition amount of the radical polymerization inhibitor, benzotriazoles, and / or carboxybenzotriazoles is preferably 0.001 to 3% by mass based on the total solid content of the photosensitive resin composition, and more preferably the lower limit. Is 0.05% by mass, and a more preferable upper limit is 1% by mass. The total addition amount is preferably 0.001% by mass or more from the viewpoint of imparting storage stability to the photosensitive resin composition, and preferably 3% by mass or less from the viewpoint of maintaining sensitivity.

｛式中、Ａ_３は、−ＣＨ（ＣＨ_３）ＣＨ_２−、−ＣＨ_２ＣＨ（ＣＨ_３）−及び／又は−ＣＨ_２ＣＨ_２−であり、ｎ_４及びｎ_５は、各々独立に０以上の整数であり、さらに好ましくは、ｎ_４及びｎ_５は、各々独立に１〜３０の整数であり、ｎ_４＋ｎ_５は１〜６０の整数であり、−（Ａ_３−Ｏ）−の繰り返し構造は、同一であるか、又は異なっていてもよく、そして−（Ａ_３−Ｏ）−の繰り返し構造が異なる場合には、ランダム又はブロックでよい。｝で表される可塑剤が挙げられる。 If necessary, the photosensitive resin composition according to the present invention may contain other plasticizers. As such a plasticizer, for example, the following general formula [III]:

{In the formula, A ₃ represents —CH (CH ₃ ) CH ₂ —, —CH ₂ CH (CH ₃ ) — and / or —CH ₂ CH ₂ —, and n ₄ and n ₅ each independently represents 0. More preferably, n ₄ and n ₅ are each independently an integer of 1 to 30, n ₄ + n ₅ is an integer of 1 to 60, and — (A ₃ —O) — repeating structures may be identical or different and have well, and - (a 3 _-O) - when the repeating structure is different can be random or block. } Is mentioned.

  In addition, for example, sorbitan derivatives such as polyoxyethylene sorbitan laurate and polyoxyethylene sorbitan oleate, polyalkylene glycols such as polyethylene glycol and polypropylene glycol, phthalic acid esters such as diethyl phthalate, and o-toluenesulfonic acid amide , P-toluenesulfonic acid amide, tributyl citrate, triethyl citrate, triethyl acetylcitrate, tri-n-propyl acetylcitrate, tri-n-butyl acetylcitrate and the like can be used. In particular, sorbitan derivatives and polyalkylene glycols are preferably used.

  It is preferable that content of the plasticizer in the photosensitive resin composition of this invention is 1-50 mass% on the basis of the total solid of the photosensitive resin composition, and a more preferable minimum is 3 mass%. A preferable upper limit is 30 mass%. It is preferably 1% by mass or more from the viewpoint of suppressing development time delay and imparting flexibility to the cured film, and preferably 50% by mass or less from the viewpoint of suppressing insufficient curing or cold flow.

<Photosensitive resin composition preparation solution>
The photosensitive resin composition according to the present invention may be a photosensitive resin composition preparation liquid to which a solvent is added. Suitable solvents include acetone, ketones typified by methyl ethyl ketone (MEK), and alcohols such as methanol, ethanol, and isopropyl alcohol. It is preferable to add a solvent to the photosensitive resin composition so that the viscosity of the photosensitive resin composition preparation liquid is 500 to 4000 mPa · sec at 25 ° C.

<Photosensitive resin laminate>
The photosensitive resin laminate according to the present invention includes a support and a layer made of the photosensitive resin composition of the present invention (hereinafter also referred to as “photosensitive resin layer”). If necessary, the photosensitive resin laminate of the present invention may have a protective layer on the surface opposite to the support. The support body should just support the photosensitive resin layer. The support used is preferably a transparent one that transmits light emitted from the exposure light source.

  Examples of such a support include polyethylene terephthalate film, polyvinyl alcohol film, polyvinyl chloride film, vinyl chloride copolymer film, polyvinylidene chloride film, vinylidene chloride copolymer film, polymethyl methacrylate copolymer film, polystyrene film. , Polyacrylonitrile film, styrene copolymer film, polyamide film, cellulose derivative film and the like. These films can be stretched if necessary. A film having a haze value of 5 or less is preferred. The thinner the film, the more advantageous in terms of image forming property and economic efficiency, but a film having a thickness of 10 to 30 μm is preferably used because of the necessity of maintaining the strength.

  An important characteristic of the protective layer used in the photosensitive resin laminate is that the protective layer is sufficiently smaller than the support and can be easily peeled with respect to the adhesive force with the photosensitive resin layer. For example, a polyethylene film and a polypropylene film can be preferably used as the protective layer. Further, a film having excellent peelability disclosed in JP-A-59-202457 can be used. The thickness of the protective layer is preferably 10 to 100 μm, and more preferably 10 to 50 μm.

  The thickness of the photosensitive resin layer in the photosensitive resin laminate according to the present invention is preferably 5 to 100 μm, and a more preferable upper limit is 50 μm. The resolution improves as the thickness of the photosensitive resin layer approaches 5 μm, and the film strength improves as the thickness approaches 100 μm. Therefore, the thickness can be appropriately selected according to the application.

  As a method for producing the photosensitive resin laminate of the present invention by sequentially laminating the support, the photosensitive resin layer, and if necessary, the protective layer, a conventionally known method can be employed. For example, the photosensitive resin composition used for the photosensitive resin layer is prepared as the above-mentioned photosensitive resin composition preparation liquid, and first applied on a support using a bar coater or a roll coater and dried, A photosensitive resin layer made of the photosensitive resin composition is laminated on the support. Then, if necessary, a photosensitive resin laminate can be produced by laminating a protective layer on the photosensitive resin layer.

<Resist pattern formation method>
The present invention relates to a resist pattern forming method including a step of forming a resist pattern using the photosensitive resin laminate according to the present invention. The resist pattern using the photosensitive resin laminate according to the present invention can be formed by a process including a laminating process, an exposing process, and a developing process.

  An example of a specific resist pattern forming method will be described. First, a laminating process is performed using a laminator. When the photosensitive resin laminate has a protective layer, the protective layer is peeled off, and then the photosensitive resin layer is heat-pressed and laminated on the substrate surface with a laminator. In this case, the photosensitive resin layer may be laminated on only one surface of the substrate surface, or may be laminated on both surfaces as necessary. The heating temperature at this time is generally 40 to 160 ° C. Moreover, the adhesiveness with respect to the board | substrate of the obtained resist pattern improves by performing this thermocompression bonding twice or more. At this time, a two-stage laminator provided with two rolls may be used for pressure bonding, or it may be repeatedly pressed through the roll several times.

  Next, an exposure process is performed using an exposure machine. If necessary, the support is peeled off and exposed to active light through a photomask. The exposure amount is determined from the light source illuminance and the exposure time. You may measure using a photometer.

  In the exposure step, a maskless exposure method may be used. In maskless exposure, exposure is performed directly on a substrate by a drawing apparatus without using a photomask. As the light source, a semiconductor laser having a wavelength of 350 to 410 nm, an ultrahigh pressure mercury lamp, or the like is used. The drawing pattern is controlled by a computer, and the exposure amount in this case is determined by the illuminance of the exposure light source and the moving speed of the substrate.

Next, a developing process is performed using a developing device. After exposure, if a support is present on the photosensitive resin layer, this is excluded. Subsequently, the unexposed portion is developed and removed using a developer composed of an alkaline aqueous solution to obtain a resist image. As the alkaline aqueous solution, an aqueous solution of sodium carbonate (Na ₂ CO ₃ ) or potassium carbonate (K ₂ CO ₃ ) is preferable. These are selected in accordance with the characteristics of the photosensitive resin layer, but an aqueous Na ₂ CO ₃ solution having a concentration of 0.2 to 2% by mass is generally suitable. A surface active agent, an antifoaming agent, a small amount of an organic solvent for promoting development, and the like may be mixed in the alkaline aqueous solution. In addition, it is preferable to maintain the temperature of this developing solution in a development process at the constant temperature in the range of 20-40 degreeC.

  Although a resist pattern is obtained by the above-mentioned process, depending on the case, a 100-300 degreeC heating process or a 100 mJ-5J post-exposure process can also be performed. By carrying out these steps, further chemical resistance can be improved. A heating furnace of a hot air, infrared ray, far infrared ray, or the like can be used for heating, and an ultra-high pressure mercury lamp or the like can be used for the post-exposure process.

<Method for manufacturing printed wiring board>
The manufacturing method of the printed wiring board which concerns on this invention includes the process of forming a resist pattern on the circuit formation board | substrate using the photosensitive resin laminated body of this invention. The circuit forming substrate is a substrate for forming a circuit such as a printed wiring, and may be, for example, a copper clad laminate or a flexible substrate. After the resist pattern is formed on the copper-clad laminate or the flexible substrate by the above-described resist pattern forming method, the printed wiring board according to the present invention is obtained through the following steps.

  First, a step of forming a conductor pattern on the copper surface of the substrate exposed by development using a known method such as an etching method or a plating method is performed. Thereafter, a peeling process for peeling the resist pattern from the substrate with an aqueous solution having alkalinity stronger than the developer is performed to obtain a desired printed wiring board. The alkaline aqueous solution for peeling (hereinafter also referred to as “peeling solution”) is not particularly limited, but an aqueous solution of sodium hydroxide (NaOH) or potassium hydroxide (KOH) having a concentration of 2 to 5% by mass is generally used. Used. A small amount of a water-soluble solvent can also be added to the stripping solution. In addition, it is preferable that the temperature of this peeling liquid in a peeling process is the range of 40-70 degreeC.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto.

(Examples 1-10, Comparative Examples 1-2)
First, a method for producing samples for evaluation of Examples and Comparative Examples will be described, and then an evaluation method and evaluation results for the obtained samples will be shown.

1. Production of Evaluation Samples Evaluation samples in Examples and Comparative Examples were produced as follows.
<Preparation of photosensitive resin laminate>
The raw materials shown in the following Table 1 (however, the numbers of each component indicate the blending amount (part by mass) as a solid content) and the solvent are sufficiently stirred and mixed to form a photosensitive resin composition preparation liquid, as a support A polyethylene terephthalate film having a thickness of 16 μm was prepared, and the photosensitive resin composition preparation liquid was uniformly applied to the surface of the polyethylene terephthalate film using a bar coater, and dried for 150 seconds in a dryer at 95 ° C. to be photosensitive. A resin layer was formed. The thickness of the photosensitive resin layer was 25 μm.
Next, a 19 μm thick polyethylene film was bonded as a protective layer on the surface of the photosensitive resin layer on which the polyethylene terephthalate film was not laminated to obtain a photosensitive resin laminate.

The details of the material components B-1 to S-2 in the photosensitive resin composition preparation liquid represented by abbreviations in Table 1 are as follows.
B-1: Ternary copolymer (methacrylic acid 25% by mass, methyl methacrylate 50% by mass, styrene 25% by mass (weight average molecular weight 50,000, acid equivalent 344)
B-2: Ternary copolymer (methacrylic acid 25% by mass, methyl methacrylate 65% by mass, butyl acrylate 10% by mass (weight average molecular weight 80,000, acid equivalent 344)
B-3: Ternary copolymer (methacrylic acid 25% by mass, methyl methacrylate 65% by mass, butyl acrylate 10% by mass (weight average molecular weight 110,000, acid equivalent 344)
B-4: Ternary copolymer of 23% by mass of methacrylic acid, 67% by mass of methyl methacrylate and 10% by mass of butyl acrylate (weight average molecular weight 200,000, acid equivalent 370)
B-5: Ternary copolymer of 25% by mass of methacrylic acid, 65% by mass of benzyl methacrylate and 10% by mass of 2-ethylhexyl acrylate (weight average molecular weight 50,000, acid equivalent 344)
B-6: Binary copolymer of 20% by mass of methacrylic acid and 80% by mass of benzyl methacrylate (weight average molecular weight 53,000, acid equivalent 429)

M-1: Polymethacrylate dimethacrylate obtained by adding an average of 2 units of ethylene oxide to both ends of bisphenol A M-2: Trioxyethyltrimethylolpropane triacrylate M-3: ε-caprolactone modified tris (acryloxyethyl) ) Isocyanurate M-4: Dimethacrylate M-5 of polyalkylene glycol obtained by adding an average of 2 units of propylene oxide and an average of 15 units of ethylene oxide to both ends of bisphenol A, respectively: Dimethacrylate M-6 of urethane polyoxypropylene glycol : Polyalkylene glycol dimethacrylate M-7: 4-nonylphenylheptaethyleneglycol with an average of 3 units of ethylene oxide added to both ends of propylene oxide of an average of 12 units Dipropylene glycol acrylate M-8: Polyethylene glycol dimethacrylate M-9 with an average of 9 units of ethylene oxide each having an average of 5 units of ethylene oxide added to both ends of bisphenol A with hydrogen added to the phenyl group Glycol diacrylate M-10: Polyethylene glycol dimethacrylate M-11 having bisphenol A added to each end with an average of 5 units of ethylene oxide. Both ends of bisphenol A have an average of 2 units of propylene oxide and an average of 6 units. Polyalkylene glycol dimethacrylate added with ethylene oxide

I-1: 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer I-2: 4,4′-bis (diethylamino) benzophenone I-3: N-phenylglycine

D-1: Malachite Green D-2: Leuco Crystal Violet

P-1: Polyoxypropylene-2-ethylhexyl ether (manufactured by Lion Corporation, Leocon 1015H)
P-2: Polyoxyethylene polyoxypropylene-2-ethylhexyl ether (manufactured by Lion Corporation, Leocon 1020H)
P-3: Polyoxypropylene butyl ether (Leoncon 1015B, manufactured by Lion Corporation)
P-4: Polyoxyethylene methyl ether (manufactured by NOF Corporation, UNIOX M-550)
P-5: Polyoxyethylene polyoxypropylene nonyl ether (manufactured by Toho Chemical Co., Ltd., Neoscore 2326)
P-6: Polypropylene glycol (Sanix PP-2000, manufactured by Sanyo Chemical Industries, Ltd.)
P-7: Polyoxyethylene sorbitan trioleate (Nippon Emulsifier Co., Ltd., New Coal 3-85)
P-8: p-Toluenesulfonic acid amide

S-1: Nitrosophenylhydroxyamine aluminum salt S-2: (N, N-dibutylamino) carboxybenzotriazole

2. Evaluation criteria
Aggregation:
The photosensitive resin layer 0.24 m ² produced by the above method was dissolved in 200 ml of a 1% by mass Na ₂ CO ₃ aqueous solution and stirred with a mixer device for 1 minute. The liquid was collected, placed in a 200 ml standard bottle and allowed to stand for 3 days, and aggregates generated in the liquid were collected by suction filtration. The aggregates were dried and then weighed, and the results were ranked as follows.
○: Aggregate is 100 mg or less ×: Aggregate exceeds 100 mg

Foamability 1:
The photosensitive resin layer 0.048 m ² produced by the above method was dissolved in 120 ml of 1% by mass Na ₂ CO ₃ aqueous solution. The solution was put into a 500 ml capacity gas absorption can and bubbled with 6000 ml / min nitrogen gas through a G3 glass filter. The time until the generated foam overflowed from the gas absorption can was measured, and the results were ranked as follows.
◎: Not overflow in 100 seconds ○: Over 30 seconds and overflow in 100 seconds ×: Overflow in 30 seconds

Foam 2:
The photosensitive resin laminate produced by the above method was exposed with an ultrahigh pressure mercury lamp (OMW Seisakusho, HMW-801) at an exposure amount of 30 mJ / cm ² . Thereafter, the support and the protective layer were removed, and 0.01 m ² was immersed in 50 ml of 3% NaOH aqueous solution in a screw tube having a capacity of 100 ml, and stirred for 30 minutes. Then, the height of the foam which remained 1 minute after shaking a screw pipe | tube well and bubbling the liquid was measured, and the result was ranked as follows.
◎: Bubble height of 10 mm or less ○: Bubble height of over 10 mm to 20 mm or less ×: Bubble height of over 20 mm

Resolution:
As a substrate for evaluation, a 1.2 mm-thick copper-clad laminate in which 35 μm-thick rolled copper foil was laminated was used, and the surface was wet buffol polished (manufactured by 3M Co., Ltd., Scotch Bright (registered trademark) HD # 600, 2 times. Through).

  After surface preparation, the copper clad laminate is preheated to 60 ° C and laminated at a roll temperature of 105 ° C using a hot roll laminator (Asahi Kasei Co., Ltd., AL-700) while peeling the polyethylene film of the photosensitive resin laminate. did. The air pressure was 0.35 MPa, and the laminating speed was 1.5 m / min.

The evaluation substrate that had passed 15 minutes after the lamination was exposed through a line pattern mask in which the width of the exposed portion and the unexposed portion was 1: 1. The mask was placed on a polyethylene terephthalate film as a support, and an ultrahigh pressure mercury lamp (manufactured by Oak Seisakusho, HMW-801) was used. The exposure amount was 30 mJ / cm ² .

After peeling the polyethylene terephthalate film from the evaluation substrate 10 minutes after the exposure, a 1% by weight aqueous solution of Na ₂ CO _{3 at} 30 ° C. is sprayed for a predetermined time using an alkali developing machine (manufactured by Fuji Kiko Co., Ltd., a dry film developing machine). The unexposed portion of the photosensitive resin layer was dissolved and removed in a time twice as long as the minimum image time. At this time, the minimum time required for completely dissolving the photosensitive resin layer in the unexposed portion was defined as the minimum development time.

The minimum mask width in which the cured resist line was normally formed was defined as the resolution value, and the resolution was ranked as follows.
A: The resolution value is 50 μm or less.
○: The resolution value exceeds 50 μm and is 100 μm or less.

3. Evaluation results The evaluation results of Examples and Comparative Examples are shown in Table 1 above.
As is clear from Table 1, in Examples 1 to 8, the constitution of the present invention was adopted to successfully improve the cohesiveness, foamability 1 and foamability 2. Since Comparative Example 1 does not contain the compound represented by (d) the general formula [I], the cohesiveness and foamability are not excellent. It can be seen that Comparative Example 2 has good cohesiveness but insufficient foamability.

  The present invention can be used for manufacturing printed wiring boards.

Claims (6)

(A) alkali-soluble thermoplastic polymer: 20 to 90% by mass,
(B) addition polymerizable monomer having at least one polymerizable ethylenically unsaturated bond in the molecule: 5 to 75% by mass;
(C) Photopolymerization initiator: 0.01 to 30% by mass, and (d) the following general formula [I]
_{R 1 -O- (A 1 -O)} n1 -H [I]
{Wherein, R ₁ is a monovalent organic group having 1 to 8 carbon atoms, A ₁ is an alkylene group, n 1 is an integer of 1 to 60, and — (A ₁ — The repeating structure of O) — may be the same or different, and may be random or block if the repeating structure of — (A ₁ —O) — is different. }
Compound represented by: 0.01 to 30% by mass
A photosensitive resin composition comprising: The addition polymerizable monomer (b) having at least one polymerizable ethylenically unsaturated bond in the molecule is represented by the following general formula [II]:

{Wherein R ₂ and R ₃ are each independently H or CH ₃ , and A ₂ is —CH (CH ₃ ) CH ₂ —, —CH ₂ CH (CH ₃ ) — and / or —CH _2. CH ₂ —, n ₂ and n ₃ are each independently an integer of 1 or more, n ₂ + n ₃ is an integer of 2 to 60, and the repeating structure of — (A ₂ —O) — is Random or block. }
The photosensitive resin composition of Claim 1 which is a bisphenol A type | system | group (meth) acrylate compound represented by these.   The photosensitive resin composition according to claim 1, wherein the (a) alkali-soluble thermoplastic polymer contains at least a monomer having styrene and an ethylenic double bond as components.   The photosensitive resin laminated body containing the layer which consists of a support body and the photosensitive resin composition of any one of Claims 1-3.   The formation method of a resist pattern including the process of forming a resist pattern using the photosensitive resin laminated body of Claim 4.   The manufacturing method of a printed wiring board including the process of forming a resist pattern on the circuit formation board | substrate using the photosensitive resin laminated body of Claim 4.